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Absolute rate constants for radical rearrangements in liquids obtained by muon spin rotation. Substituent effects on ring fission and cyclization reactions
Author(s) -
Burkhard Peter,
Roduner Emil,
Fischer Hanns
Publication year - 1985
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550170108
Subject(s) - chemistry , muonium , muon spin spectroscopy , arrhenius equation , radical , reaction rate constant , ring (chemistry) , muon , steric effects , hydrogen , stereochemistry , activation energy , nuclear physics , physics , organic chemistry , quantum mechanics , kinetics
By addition of the light hydrogen isotope muonium (Mu = μ + e − ) the 1‐ethyl‐hexen‐1‐yl radicals CH 2 = CHCH 2 CH 2 CH 2 CHCH 2 Mu, CH 2 = CHOCH 2 CH 2 CHCH 2 Mu, and CH 2 = CHCH 2 CH 2 OCHCH 2 Mu are generated in liquids. Their Fourier transform muon spin rotation spectra show linewidths increasing with increasing temperature which are attributed to the ring closure reactions. Analysis yields the absolute rate constants and their Arrhenius parameters. Together with previously reported results on analogous cyclization and on related ring fission reactions they are discussed in terms of steric and electronic effects on the reaction pathways and compared with predictions of semiempirical calculations.